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United States Patent |
5,604,266
|
Mushovic
|
February 18, 1997
|
Cured unsaturated polyest-polyurethane highly filled resin materials and
process for preparing them
Abstract
The present invention is directed to a rigid or semirigid, filled resin
material having a continuous phase which is a matrix containing a complex
crosslinked network having an unsaturated polyester-polyurethene
containing resin having fine multisize reinforcing particles and dispersed
filler particles dispersed therein. The polyester-polyurethene network of
the complex crosslinked network may interact with other polymer networks
in the continuous phase either by crosslinking or by forming an
interpenetrating polymer network. The complex crosslinked network
immobilizes the fine multisize reinforcing particles and reacts with at
least a surface layer of the dispersed filler particles. The present
invention is also directed to a process for preparing the above rigid or
semirigid, lightweight resin material, and to a composition for use in
this process. The material of the present invention is useful in a variety
of applications, and can be easily varied and modified to include a wide
variety of fine multisize reinforcing particles and dispersed filler
particles, and to function in a wide variety of uses.
Inventors:
|
Mushovic; John N. (Salt Point, NY)
|
Assignee:
|
Ecomat, Inc. (Poughkeepsie, NY)
|
Appl. No.:
|
632573 |
Filed:
|
April 15, 1996 |
Current U.S. Class: |
521/122; 521/123; 521/137; 521/172; 521/173; 523/218; 523/219 |
Intern'l Class: |
C08J 009/32; C08G 018/34 |
Field of Search: |
521/122,123,137,172,173
523/218,219
|
References Cited
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| |
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| |
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|
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|
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|
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| |
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| |
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| |
Other References
Edwards, "The Application of Isophtalic Unsaturated Polyester Urethane
Hybrids in Conventional Molding Techniques," 42nd Annual Conference
Composites Institute, The Society of the Plastics Industry, Inc., pp. 1-6,
Session 8-C Feb. 2-6, 1987.
"Interpol 5118", Cook Composites and Chemicals, Inc.
"Interpol 5124", Cook Composites and Chemicals, Inc.
"Interpol 5116", Cook Composites and Chemicals, Inc.
Aluminum Company of America, Material Safety Data Sheet for "Red Mud."
Newsfocus, Industry and Newsfocus, Technology Plastics Technology, Dec.
1992, pp. 14 and 74.
American Electric Power Service Corporation National Safety Data Sheet (Fly
Ash).
K. Ashida, Polyisocyanurate Foams, Preparation of Modified Polyisocyanurate
Foams, vol. 6, pp. 112-124.
F. A. Shutov, Hollow Sphere Fillers, Syntactic Polymer Foams, vol. 16, pp.
356-359.
Sample Resin Formulations, Formulating Hybrid Resin Molding Compounds,
Formulating Hydroxyl-Terminated Unsaturated Isopolyesters, What are Hybrid
Resins?5
Gray, Esq.; Bruce D.
Kilpatrick & Cody
|
Primary Examiner: Foelak; Morton
Attorney, Agent or Firm: Gray, Esq.; Bruce D.
Kilpatrick & Cody
Parent Case Text
The present application is a continuation-in-part of Ser. No. 08/348,973,
filed Nov. 28, 1994now U.S. Pat. No. 5,508,315, which is a continuation of
Ser. No. 08/224,775, filed Apr. 8, 1994, now U.S. Pat. No. 5,369,147,
which is a continuation-in-part of Ser. No. 07/961,332, filed Oct. 15,
1992, now U.S. Pat. No. 5,302,634. The entire contents of each of these
applications is hereby incorporated by reference.
Claims
What is claimed is:
1. A rigid or semirigid filled resin material, comprising:
(A) a continuous phase comprising a matrix comprising a complex crosslinked
network comprising an unsaturated polyester-polyurethane containing resin,
wherein said unsaturated polyester-polyurethane containing resin is the
reaction product of reaction components comprising an unsaturated
polyester polyol, a saturated polyol, a poly- or diisocyanate, and a
reactive monomer, and wherein said matrix optionally further comprises:
(1) polyurethane modified hybrid networks;
(2) networks of polymerization products of reactive monomers;
(3) networks of polymerization products of saturated polyester polyol and
poly- or diisocyanates;
(4) other networks that may form before, during, or after the formation of
the polyester-polyurethane containing resin; or
(5) mixtures of the above networks; and
(B) a dispersed phase comprising:
(1) fine multisize reinforcing particles dispersed in said matrix of said
continuous phase; and
(2) dispersed filler particles different from said fine multisize
reinforcing particles, and having a surface region bonded to said matrix.
2. The rigid or semirigid filled resin material according to claim 1,
wherein said unsaturated polyester-polyurethane containing resin has been
at least partially crosslinked with a reactive monomer.
3. The rigid or semirigid filled resin material according to claim 1,
wherein said unsaturated polyester-polyurethane containing resin has been
at least partially crosslinked with poly- or diisocyanate.
4. The rigid or semirigid filled resin material according to claim 1,
wherein said matrix comprises an interpenetrating polymer network.
5. The rigid or semirigid filled resin material according to claim 1,
wherein said matrix further comprises a polyurethane network obtained by
the reaction of a diisocyanate or polyisocyanate with a saturated
polyester or polyether polyol.
6. The rigid or semirigid filled resin material according to claim 1,
wherein said matrix further comprises a modified polyurethane hybrid resin
obtained by the reaction of a polyisocyanate, an unsaturated polyester
polyol, a saturated polyester or polyether polyol, and styrene monomer in
the presence of a free radical initiator.
7. The rigid or semirigid filled resin material according to claim 1,
wherein said continuous phase further comprises a flame retardant.
8. The rigid or semirigid filled resin material according to claim 5,
wherein said flame retardant comprises a halogenated diol or polyol.
9. The rigid or semirigid filled resin material according to claim 1,
wherein said multisize reinforcing particles have a particle size in the
range of submicron to 200 microns.
10. The rigid or semirigid filled resin material according to claim 1,
wherein said multisize reinforcing particles are selected from the group
consisting of slate dust, treated red mud, aluminum hydrates, alkaline
earth metal carbonates, calcium sulfate, metal borates, feldspars, clays,
kaolinite, bentonite, beidellite, hydroxides, fly ash, diatomaceous earth,
broken or cracked microballoons, broken or cracked microspheres,
cenospheres separated from fly ash, Fullers earth, wood flour, cork dust,
cotton flock, wool felt, shredded or finely powdered cornstalks, finely
ground nut shells, and mixtures thereof.
11. The rigid or semirigid filled resin material according to claim 1,
wherein said multisize reinforcing particles are selected from the group
consisting of slate dust, treated red mud, aluminum hydrates, metal
borates, feldspars, clays, kaolinite, bentonite, beidellite, hydroxides,
fly ash, diatomaceous earth, broken or cracked microballoons, broken or
cracked microspheres, cenospheres separated from fly ash, Fullers earth,
cork dust, cotton flock, wool felt, shredded or finely powdered
cornstalks, finely ground nut shells, and mixtures thereof.
12. The rigid or semirigid filled resin material according to claim 1,
wherein said multisize reinforcing particles are selected from the group
consisting of treated red mud, aluminum hydrates, metal borates,
feldspars, clays, kaolinite, bentonite, beidellite, hydroxides, and
mixtures thereof.
13. The rigid or semirigid filled resin material according to claim 1,
wherein said reinforcing particles are selected from the group consisting
of diatomaceous earth, broken or cracked microballoons, broken or cracked
microspheres, cenospheres separated from fly ash, Fullers earth, cork
dust, cotton flock, wool felt, shredded or finely powdered cornstalks,
finely ground nut shells, and mixtures thereof.
14. The rigid or semirigid filled resin material according to claim 1,
wherein said dispersed filler particles are selected from the group
consisting of thermoplastic particulate material, thermoset particulate
material, elastomeric particulate material, inorganic particulate
material, and mixtures thereof.
15. The rigid or semirigid filled resin material according to claim 14,
wherein said dispersed filler particles are said thermoplastic particulate
material, and are ground chlorinated polyvinyl chloride.
16. The rigid or semirigid filled resin material according to claim 14,
wherein said dispersed filler particles are said particulate thermoset
material, and are ground reinforced polyurethane or ground polyester
filled thermoset scrap.
17. The rigid or semirigid filled resin material according to claim 14,
wherein said dispersed filler particles are said elastomeric particulate
material, and are ground rubber.
18. The rigid or semirigid filled resin material according to claim 14,
wherein said dispersed filler particles are said inorganic particulate
material, and are slate particles or chips, glass, or sand.
19. The rigid or semirigid filled resin material according to claim 1,
wherein said dispersed filler particles are selected from the group
consisting of mineral fillers, ceramic flock, chopped glass, chopped
polymer fiber, directional or nondirectional glass fabrics, steel, finely
ground powdered rubber, and mixtures thereof.
20. The rigid or semirigid filled resin material according to claim 19,
wherein said mineral filler is selected from the group consisting of
silicate, asbestos, calcium carbonate, calcium sulfate, mica, barytes,
alumina, talc, carbon black, metal oxides, quartz, novaculite silica,
garnet, saponite, calcium oxide, and mixtures thereof.
21. The rigid or semirigid filled resin material according to claim 14,
wherein said dispersed filler particles further comprise surface
modifications sufficient to enhance bonding between the dispersed filler
particles and the continuous phase matrix.
22. The rigid or semirigid filled resin material according to claim 1,
wherein said dispersed filler particles have a particle size equal to or
larger than that of said fine multisize reinforcing particles, and a
maximum particle size less than about 0.25 inches.
23. The rigid or semirigid filled resin material according to claim 1,
wherein said dispersed filler particles are present in an amount of from
15 to 75 % by weight of the total resin material.
24. The rigid or semirigid filled resin material according to claim 1,
wherein said reaction components further comprise a polymer resin-forming
compound capable of reacting with at least one of the other reaction
components, with the reaction product of the other reaction components, or
of polymerizing, to form a polymer containing network.
25. The rigid or semirigid filled resin material according to claim 24,
wherein said unsaturated polyester-polyurethane containing resin comprises
an unsaturated polyester-polyurethane-polymer containing resin, wherein
said resin is the reaction product of said other reaction components and
said polymer resin-forming compound.
26. The rigid or semirigid filled resin material according to claim 24,
wherein said complex crosslinked network further comprises (4) said other
network that may form before, during, or after the formation of the
polyester-polyurethane containing resin, and wherein said other network
comprises a network formed by the reaction or polymerization of said
polymer resin-forming compound.
27. The rigid or semirigid filled resin material according to claim 25,
wherein said unsaturated polyester-polyurethane-polymer containing resin
comprises an unsaturated polyester-polyurethane-epoxy resin which is the
reaction product of an unsaturated polyester polyol, a saturated polyester
or polyether polyol, a reactive epoxy compound, a poly- or diisocyanate,
and a reactive monomer.
28. The rigid or semirigid filled resin material according to claim 25,
wherein said unsaturated polyester-polyurethane-polymer containing resin
comprises an unsaturated polyester-polyurethane-vinyl ester resin which is
the reaction product of an unsaturated polyester polyol, a saturated
polyester or polyether polyol, a reactive vinyl ester compound, a poly- or
diisocyanate, and a reactive monomer.
29. The rigid or semirigid filled resin material according to claim 25,
wherein said unsaturated polyester-polyurethane-polymer containing resin
comprises an unsaturated polyester-polyurethane-acrylic resin which is the
reaction product of an unsaturated polyester polyol, a saturated polyester
or polyether polyol, a reactive acrylic compound, a poly- or diisocyanate,
and a reactive monomer.
30. The rigid or semirigid filled resin material according to claim 25,
wherein said unsaturated polyester-polyurethane-polymer containing resin
comprises an unsaturated polyester-polyurethane-siloxane resin which is
the reaction product of an unsaturated polyester polyol, a saturated
polyester polyether polyol, a reactive siloxane compound, a poly- or
diisocyanate, and a reactive monomer.
31. A rigid or semirigid, lightweight filled resin material according to
claim 1, wherein said continuous phase comprises cellular voids therein,
and wherein the diameter of the largest of said multisize particles is no
greater than about 33% of the average thickness of walls between said
cellular voids, and wherein at least a portion of said multisize particles
are capable of containing and releasing a blowing agent during the
formation of said polyester polyurethane resin.
32. The rigid or semirigid filled resin material according to claim 1,
which is nonfoamed, and wherein said continuous phase is substantially
free of cellular voids.
33. A process for producing the rigid or semirigid filled resin material of
claim 1, comprising:
(A) obtaining reaction components comprising an unsaturated polyester
polyol, a diisocyanate or polyisocyanate, a saturated polyol, a reactive
monomer, and a free radical initiator;
(B) dry mixing fine multisize reinforcing particles with dispersed filler
particles different from said fine multisize reinforcing particles and
having a surface region capable of bonding with one or more of said
reaction components or with a network formed by said reaction components,
or with a matrix formed by said network;
(C) introducing at least one liquid reaction component to the dry mixture
obtained in (B) in an amount sufficient to wet out the dry mixture;
(D) mixing the remaining reaction components obtained in (A) with the
wetted out dry mixture obtained in (C);
(E) reacting the reaction mixture obtained in (D).
34. The process for producing the rigid or semirigid filled resin material
of claim 33, wherein said reacting step (E) is carried out in an extrusion
die.
35. The process for producing the rigid or semirigid filled resin material
of claim 34, wherein said extrusion die comprises a screw extruder.
36. The process according to claim 33, wherein said saturated polyol is a
saturated polyester polyol.
37. The process according to claim 33, wherein said reaction components
further comprise an organic diol or polyol.
38. The process according to claim 33, wherein said multisize reinforcing
particles are selected from the group consisting of treated red mud,
aluminum hydrates, alkaline earth metal carbonates, calcium sulfate, metal
borates, feldspars, clays, kaolinite, bentonite, beidellite, hydroxides,
fly ash, diatomaceous earth, broken or cracked microballoons, broken or
cracked microspheres, cenospheres separated from fly ash, Fullers earth,
wood flour, cork dust, cotton flock, wool felt, shredded or finely
powdered cornstalks, finely ground nut shells, and mixtures thereof.
39. The process according to claim 33, wherein said multisize reinforcing
particles are selected from the group consisting of treated red mud,
aluminum hydrates, alkaline earth metal carbonates, calcium sulfate, metal
borates, feldspars, clays, kaolinite, bentonite, beidellite, hydroxides,
fly ash, diatomaceous earth, broken or cracked microballoons, broken or
cracked microspheres, cenospheres separated from fly ash, Fullers earth,
cork dust, cotton flock, wool felt, shredded or finely powdered
cornstalks, finely ground nut shells, and mixtures thereof.
40. The process according to claim 33, wherein said multisize reinforcing
particles are selected from the group consisting of fly ash, diatomaceous
earth, broken or cracked microballoons, broken or cracked microspheres,
cenospheres separated from fly ash, Fullers earth, cork dust, cotton
flock, wool felt, shredded or finely powdered cornstalks, finely ground
nut shells, and mixtures thereof.
41. The process according to claim 33, wherein said reaction components
further comprise a flame retardant.
42. The process according to claim 33, wherein said flame retardant
comprises a halogenated diol or polyol.
43. The process according to claim 33, wherein said reaction components
further comprise a catalyst and surfactant.
44. The process according to claim 33, wherein said dispersed filler
particles are selected from the group consisting of thermoplastic
particulate material, thermoset particulate material, elastomeric
particulate material, inorganic particulate material, and mixtures
thereof.
45. The process according to claim 44, wherein said dispersed filler
particles are said thermoplastic particulate material, and are ground
chlorinated polyvinyl chloride.
46. The process according to claim 44, wherein said dispersed filler
particles are said thermoset particulate material, and are ground
reinforced polyurethane or ground polyester filled thermoset scrap.
47. The process according to claim 44, wherein said dispersed filler
particles are said elastomeric particulate material, and are ground
rubber.
48. The process according to claim 44, wherein said dispersed filler
particles are said inorganic particulate material, and are glass or sand.
49. The process according to claim 33, wherein said dispersed filler
particles are selected from the group consisting of mineral fillers,
ceramic flock, chopped glass, chopped polymer fiber, directional or
nondirectional glass fabrics, steel, finely ground powdered rubber, or
mixtures thereof.
50. The process according to claim 49, wherein said mineral filler is
selected from the group consisting of silicate, asbestos, calcium
carbonate, calcium sulfate, mica, barytes, alumina, talc, carbon black,
quartz, novaculite silica, garnet, saponite, calcium oxide, and mixtures
thereof.
51. The process according to claim 33, wherein said reaction components
further comprise a polymer resin-forming compound capable of reacting with
at least one of the other reaction components, with the reaction product
of the other reaction components, or of polymerizing, to form a polymer
containing network.
52. The process according to claim 51, wherein said polymer resin-forming
compound comprises a reactive epoxy compound.
53. The process according to claim 51, wherein said polymer resin-forming
compound comprises a reactive vinyl ester compound.
54. The process according to claim 51, wherein said polymer resin-forming
compound comprises a reactive acrylic compound.
55. The process according to claim 51, wherein said polymer resin-forming
compound comprises a reactive siloxane compound.
56. The process according to claim 33, wherein at least a portion of said
multisize particles added during step (B) contain a blowing agent, and
release said blowing agent during the formation of said polyester
polyurethane resin; wherein said reacting step (E) does not include
appreciable crosslinking of the reaction mixture, and further comprising:
(F) simultaneously with said reaction, foaming said reaction mixture in the
presence of said blowing agent, to form a ductile, lightweight filled
resin foam, wherein said blowing agent is released into the reaction
system from said fine multisize reinforcing particles; and
(G) hardening said ductile lightweight filled resin foam either
immediately, or at a future time, by crosslinking to a rigid or semirigid
filled foam.
57. The process according to claim 56, wherein said blowing agent is
selected from the group consisting of water, trichloromono-fluoromethane,
dibromodifluoromethane, dichlorodifluoro-methane,
dichlorotetrafluoroethane, monochlorodifluoro-methane,
trifluoroethylbromide, dichloromethane, methylene chloride, and mixtures
thereof.
58. The process according to claim 57, wherein said blowing agent comprises
water.
59. The process according to claim 57, wherein the fine multisize
reinforcing particles hold water at different energy levels within the
particles, combine water with oxides to form a range of reactive
hydroxides, trap water in spongy, foamy cenospheres, contain adsorbed
water on diverse carbon particles, or influence water release by organic
residues, polycyclic aromatic hydrocarbons, or polynuclear aromatic
hydrocarbons.
60. The process according to claim 56, wherein said blowing agent is water
and wherein said multisize reinforcing particles are selected from the
group consisting of treated red mud, aluminum hydrates, feldspars, clays,
kaolinite, bentonite, beidellite, hydroxides, and mixtures thereof.
61. The process according to claim 56, wherein said multisize reinforcing
particles are selected from the group consisting of fly ash which has been
preloaded with a blowing agent, diatomaceous earth, broken or cracked
microballoons, broken or cracked microspheres, cenospheres separated from
fly ash, Fullers earth, cork dust, cotton flock, wool felt, shredded or
finely powdered cornstalks, finely ground nut shells, and mixtures thereof
.
Description
BACKGROUND OF THE INVENTION
1. Field Of The Invention
The present invention is directed to a rigid or semirigid filled resin
material comprising a particular resin system comprising an unsaturated
polyester-polyurethane containing resin network, which forms a continuous
phase matrix, and a dispersed phase within said matrix, comprising fine
multisize reinforcing particles and dispersed filler particles, at least a
portion of which have reacted with the matrix.
The present invention is also directed to a method of preparing this rigid
or semirigid filled resin material.
Further, the rigid or semirigid filled resin material may be in the form of
a foamed resin when the fine multisize reinforcing particles are capable
of entraining a blowing agent and releasing it at different energy levels.
The present invention is also directed to this foamed material and methods
for its manufacture.
2. Discussion Of Related Art
The general manufacturing thrust in the polyester and vinyl ester polymer
industry in the area of composite materials has been to use the polyester
and vinyl ester polymers in glass reinforced structures. In addition,
styrene can be used with many polyesters, vinyl esters, and other polymer
systems.
Hybrid resins are known, and are described in Edwards, The Application Of
Isophthalic Unsaturated Polyester Urethane Hybrids In Conventional Molding
Techniques, 42nd Annual Conference Composites Institute, The Society Of
The Plastics Industry, Inc., Feb. 2-6, (1987) (pp. 1-6, Session 8-C), U.S.
Pat. No. 4,822,849, U.S. Pat. No. 4,892,919 and U.S. Pat. No. 5,086,084.
Interpenetrating polymer networks, or IPNs are also known. An IPN is a
material which consists of a pair of networks, at least one of which has
been synthesized and/or crosslinked in the presence of the other. An IPN
can be described as an intimate mixture of two or more distinct
crosslinked polymer networks that cannot be physically separated.
Interpenetrating polymer networks can be classified into several
categories. For example, when only one polymer is crosslinked and the
other is linear, the product is called semi-IPN. U.S. Pat. No. 4,302,553
discloses two structurally different crosslinked polymers, which when
combined, form an IPN structure. The IPN structure is comprised of the two
different crosslinking polymers which are permanently entangled with one
another and characterized in that no chemical interaction had occurred
between the individual networks. Interpenetrating polymer networks are
also described in U.S. Pat. No. 4,923,934 and U.S. Pat. No. 5,096,640.
U.S. Pat. No. 4,356,037 discloses the preparation of an abrasion resistant
coating containing a resin, and dispersed therein first abrasion resistant
particles of substantially uniform size, and second abrasion resistant
particles of substantially uniform size and having diameters of less than
15.4% of the first particles. This patent does not disclose or suggest the
particular unsaturated polyester-polyurethane containing resin system used
in the present invention, does not teach or suggest the use of fine
multisize reinforcing particles, and does not teach or suggest that the
particles be capable of reacting with the matrix.
U.S. Pat. No. 5,286,776 discloses a reinforced polypropylene resin
composite containing reinforcing glass fibers and particles of hard mica.
This patent does not teach the unsaturated polyester-polyurethane
containing resin matrix of the present invention, or disclose dispersed
filler particles that are bondable to the resin matrix.
U.S. Pat. No. 5,225,457 discloses a method of processing reinforced
polymers wherein base polymers are reinforced by macro short fibers and
micro short fibers. This patent does not teach the unsaturated
polyester-polyurethane containing resin matrix of the present invention.
U.S. Pat. No. 4,871,789 discloses a filled polymer composition having a
polyurethane or polyurea matrix, and containing a reinforcing filler and a
supplementary filler comprising a wollastonite or inorganic particle
having a particular aspect ratio and particle size. This patent does not
teach or suggest the unsaturated polyester-polyurethane containing resin
of the present invention.
Foamed and/or cured foams of polymer resins, which may contain inorganic
fillers, are described in U.S. Pat. No. 2,642,403, U.S. Pat. No.
3,697,456, U.S. Pat. No. 4,331,726, U.S. Pat. No. 4,725,632, U.S. Pat. No.
4,777,208, U.S. Pat. No. 4,816,503, U.S. Pat. No. 4,216,294, U.S. Pat. No.
4,260,538, U.S. Pat. No. 4,694,051, and U.S. Pat. No. 4,946,876.
Despite this activity, the products produced by the prior art, especially
products of lightweight construction materials, do not have sufficiently
well-balanced properties with regard to structural strength, as well as
with regard to corrosion and thermal resistance, and ease of processing.
Preparation of foams of unsaturated polyesters useful in the manufacture of
lightweight building materials has been attempted using a number of
different techniques. However, a difficulty encountered in attempts to
produce unsaturated polyester foams is the generation of gases so as to
cause a uniform expansion of the resin at ambient temperatures before any
appreciable crosslinking occurs. The present inventor has discovered that
with a two polymer system, a significant portion of the crosslinking and
curing does not have to occur immediately after the maximum amount of
gases has been released. Indeed, upon completion of the first polymer
reaction, the crosslinking reaction can be delayed for hours. However,
should appreciable crosslinking occur before maximum gas release, the
accompanying exothermic reaction will cause cracking as the previously
unreleased gases are generated, thereby causing stresses against a very
rigid crosslinked structure which is unable to further expand without the
loss of integrity of cell walls. Moreover, should the polyurethane
reaction have not occurred to a point sufficient to maintain the cell
structures, the gases will gradually escape, and the expanded resin will
drop back to its original state. The cured polymer will form much like a
standard resin casting, with little or no expansion.
Lightweight cementitious compositions are known in which the desired weight
reduction over concrete is achieved by the use of lightweight aggregate.
However, articles made from such materials are brittle and possess tensile
strengths which are low and limit many practical applications. Also, the
density range of lightweight concretes is 1.5 to 10 times higher than the
foam of the present invention.
Low density rigid polyurethane modified-polyisocyanurate foams have been
widely used as insulative structural members. As with other polymeric
materials, it is often desirable to reduce the polymer content and improve
the properties of these members by the addition of inorganic fillers.
Unfortunately, it has proven difficult to provide a rigid polyurethane or
polyisocyanurate foam containing more than about 10% by weight of such
fillers. These fillers tend to rupture the cells of the foam, which in
turn dramatically reduces its insulative capacity. Another undesirable
effect of high levels of fillers is that the foam becomes very friable.
Since higher filler levels are desired, because they provide a less
expensive material and certain physical property improvements, it would be
highly desirable to provide a highly filled, rigid polyurethane-modified
polyisocyanurate foam which has good insulative properties and low
friability.
U.S. Pat. No. 4,661,533 relates to using a particular inorganic filler,
namely fly ash, as the inorganic filler for filling rigid polyurethane
modified-polyisocyanurate foams. High percentage additions of fly ash to
very light weight (2 pounds per cubic foot (pcf)) insulating foam are
described. The use of the fly ash inorganic filler enables the foam to be
filled to a theoretical level of about 80% of the foam's total weight
without deterioration of the insulative properties, friability and
compressive strength. The foam is useful as board insulation, sheathing
insulation, pipe insulation and the like. However, even though the foam of
the above patent is highly filled with fly ash, the problems associated
with the formation of two distinct polymers and hybrid resin technology
where a very high percentage of the end product is crosslinkable as a
cured polyester (up to 90%) did not have to be addressed. Additionally,
the superior processing advantages inherent in the polyester/polyurethane
chemistry are not possible with the prior art product. The potential
physical properties obtainable from the filled foam of the present
invention, having two distinct polymer systems, are much higher, and the
ability to control individual reactions in the polyester/polyurethane
system used in the present invention is considerably better than that
possible with the single shot polyurethane/polyisocyanurate chemistry of
the prior art.
SUMMARY OF THE INVENTION
The present invention adopts an approach to composite polymer materials
that is completely different from that described above. By using the
hybrid polyester-polyurethane resin described below, a base resin is
obtained that allows for easy modification by inclusion of different
polymer species, and also results in bonding of dispersed filler
particles, e.g., thermoplastic scrap or thermoplastic like areas of
thermoset scrap, using a two-component or multicomponent system which
bonds to the filler particle surfaces.
It is an object of the present invention to provide multi-component polymer
systems based upon a dual polymer thermoset which forms a continuous
matrix phase, and upon the dispersion therein of filler particles, the
chemical and physical properties of which can be varied by changing
chemical and processing parameters. More specifically, it is an object of
the present invention to provide such a system which can be modified by
selection of the particular dispersed filler particles and the matrix
phase components. This modification results from the contribution of the
matrix phase components to the overall properties of the material, and
from the bonding properties between the matrix phase and the dispersed
filler particles.
It is also an object of the present invention to provide a multi-component
polymer system that avoids liquid incompatibilities during processing,
thereby increasing the adaptability of the polymer system to the inclusion
of additional components in order to adjust its properties. More
specifically, it is an object of the present invention to provide fine
multisize reinforcing particles to interfere with liquid phase separation
that may result from polyol addition incompatibility during processing.
It is another object of the present invention to provide a multi-component
polymer system which can be chemically linked to other polymer components,
by covalent bonding, crosslinking, as an IPN, or by a combination of
these, in order to provide products having desired properties.
It is a further object of the present invention to provide low cost, rigid
or semirigid polymeric compositions, both solid and foamed, which contain
very high percentages of either single or multiple organic and/or
inorganic blends of industrial byproducts and waste materials. It is a
further object of the present invention to provide such materials having
desirable physical, chemical, and environmental properties, such as good
structural strength, corrosion and thermal resistance, and related
properties, due to the properties of the matrix phase materials and the
bonding of one or more of the types of dispersed particles to the
polymeric matrix binder. More specifically, it is an object of the present
invention to provide a material wherein the bonding properties between the
polymeric matrix and the dispersed particles is specifically tailored to
provide the processing flexibility and properties desired, for example
those of traditional structural building materials.
Another object of the present invention is to provide a material which
recycles and uses large quantities of industrial waste particulates and/or
industrial waste material which can be formed into particles by grinding
or other procedures, thereby providing low cost castable or castable and
foamable materials, and decreasing disposal costs for these industrial
waste materials.
Another object of the present invention is to provide a process for
preparing the above rigid or semirigid, polymeric compositions, which can
be used with conventional, low cost processing equipment.
Another object of the present invention is to provide a rigid or semirigid,
polymeric material which can be effectively further reinforced with
mineral fillers, ceramic flock, chopped glass, chopped polymer fiber,
directional or nondirectional glass fabrics, steel, finely ground powdered
rubber, and the like, which take advantage of one or both phases to
provide this effective reinforcement.
These and other objects and advantages are obtained by the present
invention by providing a rigid or semirigid filled resin material,
comprising:
(A) a continuous phase comprising a matrix comprising a complex crosslinked
network comprising an unsaturated polyester-polyurethane containing resin,
wherein said unsaturated polyester-polyurethane containing resin is the
reaction product of reaction components comprising an unsaturated
polyester polyol, a saturated polyol, a poly- or diisocyanate, and a
reactive monomer, and wherein said matrix optionally further comprises:
(1) polyurethane modified hybrid networks;
(2) networks of polymerization products of reactive monomers;
(3) networks of polymerization products of saturated polyester polyol and
poly- or diisocyanates;
(4) other networks that may form before, during, or after the formation of
the polyester-polyurethane containing resin; or
(5) mixtures of the above networks; and
(B) a dispersed phase comprising:
(1) fine multisize reinforcing particles dispersed in said matrix of said
continuous phase; and
(2) dispersed filler particles different from said fine multisize
reinforcing particles, and having a surface region bonded to said matrix.
These objects are also obtained by providing a process for producing this
rigid filled resin material, comprising:
(A) obtaining reaction components comprising an unsaturated polyester
polyol, a diisocyanate or polyisocyanate, a saturated polyol, a reactive
monomer, and a free radical initiator;
(B) dry mixing fine multisize reinforcing particles with dispersed filler
particles different from said fine multisize reinforcing particles and
having a surface region capable of bonding with one or more of said
reaction components or with a network formed by said reaction components,
or with a matrix formed by said network;
(C) introducing at least one liquid reaction component to the dry mixture
obtained in (B) in an amount sufficient to wet out the dry mixture;
(D) mixing the remaining reaction components obtained in (A) with the
wetted out dry mixture obtained in (c);
(E) reacting the reaction mixture obtained in (D).
The objects of the present invention are also attained by providing a
composition and process as disclosed above, wherein the fine multisize
reinforcing particles contain a blowing agent which is releasable at
different energy levels, and which results in the formation of a rigid,
lightweight foamed material.
Further scope of applicability of the present invention will become
apparent from the detailed description given hereinafter. However, it
should be understood that the detailed description and specific examples,
while indicating preferred embodiments of the invention, are given by way
of illustration only, since various changes and modifications within the
spirit and scope of the invention will become apparent to those skilled in
the art from this detailed description.
DETAILED DESCRIPTION OF THE INVENTION
Multi-component polymer systems comprised of basically two polymers,
unsaturated polyesters and polyurethanes, according to the present
invention, can be manufactured in at least two ways.
First, hybrid polyols, having molecular chains containing unsaturated
polyester polyols and modified by chemical treatment so that the chain
contains hydroxyl terminations, can be combined with unsaturated polyester
promoters, reactive monomers, catalysts, and poly or diisocyanates. When
these components are mixed well and cured, both urethane and unsaturated
polyester moieties exist in the resulting polymerized structure. Examples
of these materials suitable for use in preparing the unsaturated
polyester-polyurethane material used in the present invention are
discussed in U.S. Ser. No. 08/348,973, which is hereby incorporated by
reference, and are also in more detail below.
Second, the basic ingredients that form an unsaturated polyester polymer
having hydroxy terminations, including unsaturated polyester polyols
(which need not have hydroxy terminations), promoters, catalysts, and
reactive monomers may be blended with saturated polyols and poly or
diisocyanates to form an end structure containing both unsaturated
polyester and polyurethane networks.
While the resulting molecular structures may differ, the percentages of
each polymer species may be approximately equivalent. While the first
method, using the hybrid resin, is less complex, the second method is
considerably less expensive from the standpoint of the feedstock
materials. However, either method may be used to prepare the basic
unsaturated polyester-polyurethane containing resin of the present
invention.
The percentage of each polymer structure may be varied by varying the
amounts of the various reactants added. For example, when a hybrid resin
is used, the polyurethane component may be increased by increasing the
amount of saturated polyol to the unsaturated hybrid resin, and using the
appropriate amount of poly or diisocyanate. This increase in the
percentage of polyurethane structure results in a decrease in the amount
of unsaturated polyester resin. The percentage of crosslinked polyester
resin in the network can be increased by increasing the amount of styrene
or other reactive monomer or adding additional crosslinkable polymers or
reducing the amount of saturated polyol (to reduce the fraction of
urethane component).
The unsaturated polyester-polyurethane containing resin may be at least
partially crosslinked with a reactive monomer, or a poly- or diisocyanate,
or both. The network formed by the unsaturated polyester polyurethane per
se may be entangled with the other networks described above (e.g., with a
polyurethane network obtained by reaction of a poly- or diisocyanate with
a saturated polyester polyol, or with a modified polyurethane hybrid resin
obtained by reaction of a polyisocyanate, an unsaturated polyester polyol,
a saturated polyester polyol, and styrene monomer in the presence of a
free radical initiator) to form an interpenetrating polymer network (IPN),
or may be crosslinked with these networks. Regions of IPN and crosslinking
may both exist in the same material.
The unsaturated polyester-polyurethane containing resin may also contain
domains wherein the unsaturated polyester polyurethane network is bonded
to other polymer resins, such as epoxy resins (including, e.g., bisphenol
A epoxy resins, such as, CIBA-GEIGY bisphenol A epoxy solutions), acrylic
resins (e.g., Ashland ATLAC), vinyl ester resins (e.g., Dow Duracane
411-45 or Reighhold resins), siloxane resins, or combinations of these
resins. This bonding may take the form of direct covalent bonding or
crosslinking to the other polymer resins. In addition to, or in place of
the above bonding, the unsaturated polyester polyurethane network may be
interwoven with networks of the other polymer in the form of an IPN.
Regions of both IPN and crosslinking may occur in the same matrix. These
additional polymer resins may be included by adding reaction components
known to form the particular polymer resin to the matrix resin forming
system, as discussed below.
The term "unsaturated polyester-polyurethane containing resin" is used
herein to refer to not only the unsaturated polyester-polyurethane network
per se, but to networks having regions of unsaturated
polyester-polyurethane bonded, either directly or by crosslinking, to
regions of any of the other polymer resins or other networks discussed
above. For example, a network comprising regions of unsaturated
polyester-polyurethane crosslinked or directly bonded to regions of a
network of polymerization products of a reactive monomer (e.g., styrene)
which are bonded to regions of an epoxy resin would be included within the
scope of the term "unsaturated polyester polyurethane containing resin."
It is this ability of the unsaturated polyester polyurethane network to not
only bond to the fine multisize reinforcing particles and the dispersed
filler particles, but to also allow for the easy inclusion of additional
polymer networks, which allows modification or variation of the composite
in at least two ways. First, these additional polymer networks affect the
properties of the composite due to their presence therein, by adding their
own physical and chemical properties to the system. Second, the presence
of the additional polymer resin and/or additional networks may, in
combination with certain dispersed filler particles, result in better
bonding and adhesive strengths to dispersed filler materials that
preferentially react with or bond to the particular polymer resin or
network.
The variability of the fine multisize reinforcing particles, dispersed
filler particles, and presence of additional polymers in the material
allows its physical properties to vary from a rigid material (e.g., having
a tensile elongation of about 1-2%) through a semirigid material (e.g.,
having a tensile elongation of about 5-10%) to an almost elastomeric
material.
The saturated polyol may be any polyol which forms a urethane by reaction
with isocyanates, e.g., a saturated polyester polyol, a saturated
polyether polyol, or a saturated caprolactam polyol, and organic diols or
polyols may also be included in step (A) to help form additional polymer
networks, which may also bond to the dispersed filler particles. Flame
retardants, such as those described above, may also be included in step
(A). Catalysts and surfactants may also be included in step (A).
The reactive monomer may be selected from the group consisting of styrene
monomers, vinyl monomers, and mixtures thereof. The free radical initiator
may be selected from the group consisting of azoisobutyronitrile and an
organic peroxide, such as benzoyl peroxide.
As pointed out above, the continuous phase may also contain additional
polymers, which can form their own networks, or form part of the
polyester-polyurethane network, or both. Examples of such polymers include
epoxy resins, vinyl ester resins, and siloxane resins. These polymers are
included in the continuous phase by including resin-forming materials,
such as monomers or prepolymers, in the mixture of unsaturated polyester
polyol, polyisocyanate, reactive monomer, etc., as discussed above.
The continuous phase may also contain a flame retardant, such as a
halogenated diol or polyol.
The typical mineral filler for thermoplastic and thermoset polymers is
normally characterized as a chemically pure, homogeneous solid with a
narrow particle size distribution. In contrast, the fine multisize
reinforcing particles used in the present invention may have diverse
chemical compositions and should have a wide range of particle sizes.
The fine multisize reinforcing particles may have a particle size
distribution in the range of submicron particles to sizes as large as 200
microns, more particularly a range of 0.1 to 100 microns. The particles
may be selected from the group consisting of slate dust, treated red mud,
aluminum hydrates, alkaline earth carbonates, such as calcium carbonates
or magnesium carbonates, calcium sulfate, metal borates, feldspars, clays,
kaolinite, bentonite, beidellite, hydroxides, fly ash, optionally
preloaded with a blowing agent when a foam is desired, diatomaceous earth,
broken or cracked microballoons, broken or cracked microspheres,
cenospheres separated from fly ash, Fullers earth, wood flour, cork dust,
cotton flock, wool felt, shredded or finely powdered cornstalks, finely
ground nut shells, and mixtures thereof. Slate dust and fly ash are
particularly useful in this regard.
The term "dispersed filler particles" as used herein is intended to
encompass not only particles, but also fibers and fabrics. The dispersed
filler particles are chemically bonded to the polymer matrix. This bonding
occurs in a surface region of the dispersed filler particle, which may be
the surface per se, or may extend to some depth below the surface at which
depth the particle and the matrix are capable of bonding. The dispersed
filler particles may be organic polymeric material, such as polymeric
scrap, more particularly thermoplastic, thermoset, or elastomeric
material, that has been formed into particles by crushing, grinding,
pulverizing, etc.
The dispersed filler particles may also be inorganic material, including
mineral fillers, such as slate particles or chips, silicate, asbestos,
calcium carbonate, mica, barytes, alumina, talc, carbon black, metal
oxides, quartz, novaculite silica, garnet, saponite, calcium oxide, and
mixtures thereof.
Examples of suitable materials for the dispersed filler particles include
chlorinated polyvinyl chloride, reinforced polyester or polyester filled
thermoset scrap, rubber, glass, sand, ceramic flock, such as a silica
alumina ceramic fiber or carbon fiber, chopped glass, chopped polymer
fiber, directional or nondirectional glass fabrics, steel, finely ground
powdered rubber, aramid based fibers, such as kevlar, and mixtures
thereof.
The dispersed filler particles may comprise mixtures of any of the above
materials. Further, if necessary to achieve or enhance chemical bonding
between the surface region of a particular dispersed filler particle and a
particular matrix, the surface of the filler particle may be modified by
the addition of known surface modifiers, such as silane or polymer
emulsion coatings.
Desirably, the dispersed filler particles are present in amounts of between
15 and 75% by weight, based upon the weight of the total material.
Because the fine multisize reinforcing particles have a high specific
surface area, they require more polymer matrix to immobilize them, and the
relative amounts of fine multisize reinforcing particles and dispersed
filler particles used is dependent upon the amount of total filler to be
included in the final product. For instance, when it is desired to obtain
a final filled product having about 85% by weight total filler (fine
multisize reinforcing particles and dispersed filler) based upon the
weight of the final composition, the amount of fine multisize reinforcing
particles should be around 20 to 25% by weight of the total filler amount.
When a product having greater than 85% by weight of total filler is
desired, then the fine multisize reinforcing particles should only form
about 15-20% by weight of the total filler. When a product having about
70% by weight of total filler is desired, then the fine multisize
reinforcing particles and the dispersed filler particles can be present in
amounts of about 50% by weight of the total filler. When a product having
only 60% by weight of filler is desired, then virtually any fraction of
fine multisize reinforcing particles can be used.
When a foamed product is desired, the fine multisize reinforcing particles
used in the present invention may be any particles that will reinforce the
cell walls of the foamed material, as more particularly described below,
and at least a portion of which are capable of entraining a blowing agent,
either through chemical or physical interactions, and of releasing the
blowing agent during the foaming reaction, also more particularly
described below. Desirably, the reinforcing particles possess, or are
ground to possess, a particle size distribution of submicron to 200
microns, more particularly 0.1 to 100 microns.
These reinforcing particles may be selected from treated red mud, aluminum
hydrates, feldspars, clays, shales, slates, kaolinite, bentonite,
beidellite, hydroxides, such as calcium hydroxide, or any particle having
a particle size distribution similar to that of red mud, and capable of
releasing water at various energy levels during the reaction forming the
continuous phase matrix, as more particularly described below. Mixtures of
these particles may also be used.
The reinforcing particles may also be selected from fly ash which has been
preloaded with a blowing agent, diatomaceous earth, broken or cracked
microballoons, broken or cracked microspheres, cenospheres separated from
fly ash, Fullers earth, wood flour, cork dust, cotton flock, wool felt,
shredded or finely powdered cornstalks, finely ground nut shells, and
other fine size cellular materials having a particle size distribution
similar to that of fly ash. Mixtures of these particles may also be used.
Particles such as diatomaceous earth, broken or crushed microballoons,
broken or crushed microspheres, cenospheres separated from fly ash,
Fullers earth, and wool felt should be preloaded with a blowing agent
before reaction, as is done with fly ash. Particles such as wood flour,
cork dust, cotton flock, shredded or finely powdered cornstalks, or finely
ground nut shells already contain water entrained therein, and may be used
as is, or after preloading with additional blowing agent.
Moreover, mixtures of particles from each of the above groups may be used.
The reinforcing particles for use in a foam are desirably preloaded fly
ash.
The reinforcing particles in the foam may be supplemented by mineral
fillers, chopped glass, chopped polymer fiber, directional or
nondirectional glass fabrics, steel, finely ground powdered rubber, or any
of the fine multisize reinforcing particles described above, which may or
may not be capable of entraining a blowing agent. Mineral fillers and
powdered rubber should be ground to a particle size distribution
consistent with that of the reinforcing particles, such as the particle
size distribution of fly ash or treated red mud. This supplementing of the
fine multisize reinforcing particles is in addition to the inclusion of
dispersal filler particles, as discussed above.
The continuous phase of the rigid, filled resin material according to the
present invention serves as a binder for the reinforcing particles and
filler discussed above This continuous phase comprises at least an
unsaturated polyester polyurethane hybrid resin, which forms a matrix
comprising a complex cross-linked network. The polyester polyurethane
hybrid resin is formed by reacting an unsaturated polyester polyol, a
saturated polyol, a poly- or diisocyanated and a reactive monomer, as
shown in more detail below, and may be crosslinked with either said
reactive monomer or said poly- or diisocyanate, or both. This reaction
mixture may form additional networks which may become entangled or
crosslinked with the polyester polyurethane hybrid network, and thus
incorporated into the continuous phase network. As a result the continuous
phase may also comprise, as exemplary networks polyurethane modified
hybrid networks, or networks formed from polymerization products of
reactive monomers, or networks formed from polymerization products of a
saturated polyol with a poly or diisocyanate, or other networks that may
form during the above-described reaction, or mixtures of any or all of
these networks.
These networks may individually immobilize the reinforcing particles
discussed above. Alternatively, when multiple networks are present they
may be entangled, crosslinked together, or otherwise interact, further
immobilizing the reinforcing particles. For example, the crosslinked
polyester polyurethane hybrid resin network may form an interpenetrating
polymer network, or IPN, with a second polyurethane network formed by the
reaction of a diisocyanate or polyisocyanate with a saturated polyester
polyol. Furthermore, the above-mentioned crosslinked hybrid resin may form
a modified IPN with said second polyurethane network and with a third
modified hybrid network formed by the reaction of a diisocyanate or
polyisocyanate, an unsaturated polyester polyol, a saturated polyester
polyol, and a reactive monomer.
As pointed out above, the polyester polyurethane hybrid resin network may
be entangled with other polymer networks to form an interpenetrating
polymer network, or IPN. An IPN is a material which consists of a pair or
networks, at least one of which has been synthesized and/or crosslinked in
the presence of the other. Interpenetrating polymer networks (IPN) are
more or less intimate mixtures of two or more distinct crosslinked polymer
networks that cannot be physically separated. IPN can be considered as
another technique, very much like graft or block copolymerization, for
inducing polymer blend compatibility through polymer structure
modification. The possibility of combining various chemical types of
polymeric networks has produced some IPN compositions that exhibit
synergistic behavior. If one polymer is elastomeric in nature and another
is glassy, then a reinforced rubber is obtained if the elastomer phase
predominates, and an impact-resistant plastic results if the glassy phase
predominates.
There are several categories of interpenetrating polymer networks. When
only one polymer is crosslinked and the other is linear the product is
called a semi-IPN. Semi-IPN or semi-2-IPN exists when, respectively,
polymer 1 or polymer 2 is the crosslinked component. Furthermore, in
addition to IPN--the general term for interpenetrating polymer
network--there can be distinguished the simultaneous interpenetrating
network (SIN), wherein both polymers are synthesized simultaneously, by
either addition or condensation polymerization reactions, and the
interpenetrating elastomeric network (IEN). An IEN refers to those
materials that are made by mixing and coagulating two different polymer
latexes, and crosslinking the coagulum to form a three-dimensional
structure. If the latex coagulum is not crosslinked, the resulting product
is called a latex polyblend.
In the continuous phase of the present invention, although normally
crosslinking is present within each phase, in areas where a true IPN
exists, there is no polyurethane to polyester crosslinking. This area of
the foam is called an IPN (interpenetrating polymer networks) structured
composite. IPNs are formed when polymerization compositions are
independently reacted to form distinct, intertwining, continuous polymeric
chains. Chemically combining different types of polymeric networks results
in the formation of resins having different properties. The IPN which is
produced exhibits properties that are different from the individual
constituent polymers.
As discussed above, an IPN may form in the material of the present
invention by the reaction of the unsaturated polyester polyol, which has
hydroxy terminal groups, with a diisocyanate and/or polyisocyanate and a
reactive monomer, which crosslinks the resulting polyester-polyurethane
chain, and the independent reaction of a saturated polyester polyol with
said diisocyanate and/or polyisocyanate to form a polyurethane. A modified
hybrid IPN may also form in the material of the present invention when, in
addition to the above reactions, said diisocyanate and/or polyisocyanate
forms an additional network by reaction with said unsaturated polyester
polyol, said reactive monomer, and said saturated polyester polyol. This
complex third network may intertwine with one or both of the other two
networks. Other, more complex arrangements are also possible.
For example, crosslinking between networks may occur to various degrees,
and usable structures may be formed from networks having minor degrees of
crosslinking and significant entanglement, forming IPN-like structures in
that the networks are entangled, but also contain some crosslinking.
Usable structures may also be formed from networks that have an extremely
high degree of crosslinking, e.g., between all of the polymer networks
present. This is more likely to occur with hybrid resins containing high
functionality polyisocyanates and saturated and unsaturated polyols having
large numbers of hydroxyl sites.
Hybrid resins are well-known in the art, and hybrid polyester-polyurethane
resins combine the best features of the polyester and polyurethane
technologies. The resins are tougher than polyesters, and are stronger,
stiffer and less costly than polyurethanes. Unsaturated
polyester-polyurethanes contain double bonds which can react with styrene
to form a strong, yet flexible solid.
Urethane hybrids are also versatile, and can be formulated for use in
virtually any method of molding common to the unsaturated polyester and
urethane industries. Equally important, they can be cured in a matter of
seconds at room temperature or can be molded at elevated temperatures.
They can be of low viscosity for ease of pumping or to embrace high levels
of filler and reinforcement, or they can be thickened to flow only under
high pressures and temperatures.
The weight percent range of polyurethane in the overall filled
polyester/polyurethane structure should be between about 10% and 60%.
Below 10% the contribution of the urethane to the properties of the
structure is minimal. If the urethane percentage is over 60%, some
polyester crosslinking reactions may be hindered, and manufacturing
consistency may be lost.
Unsaturated polyesters useful in forming the polyester polyol-polyurethane
hybrid resin are typically prepared as the condensation reaction products
of at least a di- or a polybasic acid, or an anhydride thereof, and a di-
or polyhydric compound, wherein at least one of said acid or anhydride, or
said di- or polyhydric compound contains ethylenic unsaturation.
Optionally, flame retardant materials may be included as a reactant in the
formation of said unsaturated polyester.
The unsaturated polyesters of the present invention are generally employed
in a proportion ranging from about 20 to 80 parts, preferably 40 to 70
parts, per 100 parts by weight based on the total weight of the curable
foamable composition, exclusive of the weight of reinforcing particles.
Typical di- or poly-basic acids or anhydrides thereof used in the
preparation of the unsaturated polyesters include, but are not limited to,
phthalic acids, iso- or terephthalic acid, adipic acid, succinic acid,
sebacic acid, maleic acid, fumaric acid, citaconic acid, chloromaleic
acid, allylsuccinic acid, itaconic acid, mesaconic acid, citric acid,
pyromellitic acid, trimesic acid, tetrahydrophthalic acid, thiodiglycollic
acid, and the like. These acids and anhydrides may be independently or
jointly used.
Typical di- or polyhydric compounds used in the preparation of the
unsaturated polyesters include, but are not limited to ethylene glycol,
diethylene glycol, triethylene glycol, propylene glycol, dipropylene
glycol, glycerol, 2-butyn-1,4-diol, neopentyl glycol, 1,2-propanediol,
pentaerythritol, mannitol, 1,6-hexanediol, 1,3-butylene glycol,
2-buten-l,4-diol, hydrogenated bisphenol A, bisphenoldioxyethyl ether,
bisphenol-dioxypropyl ether, neopentyl glycol and the like.
A variety of reactive monomers may be used. The reactive monomers may be
mixed in with the polymeric components of the composition of the present
invention in an amount sufficient to produce a thermoset product. In
general, the proportions employed range from about 10 to 25 parts by
weight, preferably 10 to 20 parts by weight per 100 parts by weight based
on the total weight of the curable composition exclusive of the weight of
reinforcing particles. Specific examples include, but are not limited to,
styrene, chlorostyrenes, methyl styrenes such as s-methyl styrene,
p-methyl styrene, vinyl benzyl chloride, divinyl benzene, indene, allyl
benzene unsaturated esters such as: methyl methacrylate, methyl acrylate
and other lower aliphatic esters of acrylic and methacrylic acids, allyl
acetate, vinyl acetate, diallyl phthalate, diallyl succinate, diallyl
adipate, diallyl sebacate, diethylene glycol bis(allyl carbonate),
triallyl phosphate and other allyl esters, and vinyl toluene, diallyl
chlorendate, diallyl tetrachlorophthalate, ethylene glycol diacrylate,
ethylene glycol dimethacrylate, ethylene glycol diethacrylate, amides such
as acrylamides, vinyl chloride, and mixtures thereof. Among these
examples, styrene is preferred.
The isocyanate component of the curable composition of the present
invention has a isocyanate functionality of two or more. The isocyanate
component may thus be a diisocyanate or polyisocyanate. The diisocyanates
or polyisocyanates of the present invention are generally employed in a
proportion ranging from about 5 to 40 parts, preferably 15 to 20 parts by
weight, per 100 parts by weight based on the total weight of the curable
composition exclusive of weight of reinforcing particles.
The diisocyanates or polyisocyanates include aliphatic, alicyclic and
aromatic types. Representative examples include 2,4-tolylenediisocyanate,
2,6-tolylenediisocyanate, 1,6-hexamethylenediisocyanate,
4,4'-diphenylmethanediisocyanate, 4,4'diphenylether-diisocyanate,
m-phenylenediisocyanate, 1,5-naphthalene-diisocyanate,
biphenylenediisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate,
dicyclohexylmethane-4,4'diisocyanate, p-xylylenediisocyanate,
m-xylylene-diisocyanate, bis(4-isocyanatophenyl) sulfone, isopropylidene
bis(4-phenylisocyanate), tetramethylene diisocyanate, isophorone
diisocyanate, ethylene diisocyanate, trimethylene diisocyanate,
propylene-1,2-diisocyanate, ethylidene diisocyanate,
cyclopentylene-1,3-diisocyanates, 1,2-,1,3- or 1,4-cyclohexylene
diisocyanates, 1,3- or 1,4-phenylene diisocyanates, polymethylene
polyphenyleneisocyanates, bis(4isocyanatophenyl) methane,
4,4'-diphenylpropane diisocyanates, bis(2-isocyanatoethyl)carbonate,
1-methyl-2,4-diisocyanatocyclohexane, chlorophenylene diisocyanates,
triphenylmethane-4,4', 4"-triisocyanate, isopropyl
benzene-.alpha.-4-diisocyanate,
5,6-diisocyanatobutylbicyclo[2.2.1]hept-2-ene, hexahydrotolylene
diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 4,4', 4"-triphenylmethane
triisocyanate, polymethylene polyphenylisocyanate,
tolylene-2,4,6-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',
5,5'-tetraisocyanate, and mixtures thereof.
The curable composition of the present invention may optionally contain di-
or polyhydric compounds, capable of reacting with the isocyanate component
to form polyurethanes.
The typical optionally contained di- or poly-hydric compounds include
ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
dipropylene glycol, glycerol, 2-butyn-1,4-diol, neopentyl glycol,
1,2-propanediol, pentaerythritol, mannitol, 1,6-hexanediol, 1,3-butylene
glycol, 2-buten-1,4-diol, hydrogenated bisphenol A, bisphenoldioxyethyl
ether, bisphenol-dioxypropyl ether, neopentyl glycol and the like and
mixtures thereof.
Examples of curing catalysts include free radical initiators, such as azo
compounds such as azoisobutyronitrile, and organic peroxides, such as
tertiary-butyl perbenzoate, tertiary butyl peroctoate, benzoyl peroxide,
methyl ethyl ketone peroxide, acetoacetic peroxide, cumene hydroperoxide,
cyclohexanone hydroperoxide, and dicumyl peroxide. Benzoyl peroxide is
preferred. The catalyst is used in an amount of 0.03 to 2.5 parts by
weight, preferably 0.5 to 1.0 parts by weight, per 100 parts by weight
based on the total weight of the curable composition, exclusive of the
weight of fine multisize reinforcing particles or dispersed filler
particles.
To accelerate the curing, a metal compound may be optionally added.
Examples include cobalt naphthenate, cobalt octanoate, divalent
acetylacetone cobalt, trivalent acetylacetone cobalt, potassium hexanoate,
zirconium naphthenate, zirconium acetylacetonate, vanadium naphthenate,
vanadium octanoate, vanadium acetylacetonate, lithium acetylacetonate and
combinations thereof. Other accelerators include tertiary amines such as
dimethylaniline, diethylaniline and dimethyl-p-toluidine.
Catalysts which promote the formation of urethane linkages by reaction of
isocyanate groups and hydroxy groups include amine compounds, such as
triethylenediamine, N-methylmorpholine, tetramethyl-1,4-butanediamine,
N-methylpiperazine, dimethylethanolamine, diethyl-ethanolamine,
triethylamine, and the like; and organometallic compounds, such as
stannous octanoate, dibutyltin dilaurate, dibutyltin di-2-ethylhexanoate,
and the like. These may be used alone or in combination with one another.
The catalyst can be used in a broad range of amounts, usually 0.03 to 2.0
parts by weight, preferably 0.02 to 1.0 parts by weight, per 100 parts by
weight based on the total weight of the curable composition, exclusive of
the weight of reinforcing particles.
The foaming or blowing agent which may be optionally added to the curable
foamable composition of the present invention includes water or a
low-boiling volatile liquid. Examples of low-boiling volatile liquids are
halogenated hydrocarbons which include trichloromonofluoromethane,
dibromodifluoromethane, dichlorodifluoromethane,
dichlorotetrafluoroethane, monochlorodifluoromethane,
trifluoroethylbromide, dichloromethane, methylene chloride, and the like.
These may be used alone or in combination with one another. Other
conventional foaming or blowing agents are also within the scope of this
invention.
Fire retardant raw materials may optionally be included as a reactant in
the preparation of the unsaturated polyester polyol component, of the
polyurethane component, or of both. Alternatively, these flame retardant
raw materials may simply be physically mixed and become part of a
dispersed ingredient in the composition of the present invention.
Fire retardant materials which may be used as reactants in the preparation
of the unsaturated polyesters include tetrachlorophthalic anhydride,
tetrabromophthalic anhydride, dibromotetrahydrophthalic anhydride,
chlorendic acid, tetrabromobisphenol A, dibromoneopentyl glycol and the
like. Said fire retardant materials are preferably contained in a
proportion ranging from 5 to 40, preferably 15-20 parts by weight based on
the total weight of the curable composition, exclusive of the weight of
the reinforcing particles.
The hybrid cured material of the present invention may also contain
non-reactive halogen-containing material in a proportion ranging from
about 5 to 20 parts, preferably about 5 to 10 parts by weight, per 100
parts by weight based on the total weight of the curable composition
exclusive of the weight of reinforcing particles or dispersed filler
particles. These non-reactive halogen-containing materials include organic
and/or inorganic materials. The organic materials include halogenated
aliphatic, cycloaliphatic, cyclic and aromatic hydrocarbons. Illustrative
are tetrachlorobutane, tetrabromobutane, hexabromoethane, chlorendic
anhydride, tetrahalogenated phthalic anhydride, tetrabromocyclooctane,
tetrachlorocyclooctane, hexachlorocyclopentadiene, hexabromocyclododecane,
hexachlorocyclododecane, hexabromocyclohexane, pentabromotoluene, and the
halogenated bi- and polyphenyl aromatic compounds. Halogenated polymeric
materials are also useable. Inorganic materials include metal oxides, such
as antimony oxides, iron oxides, copper oxides, titanium oxides and
mixtures thereof. Illustrative examples include antimony trioxide,
antimony tetraoxide, antimony pentoxide, ferric oxide, cupric oxide,
titanium dioxide, etc.
Coupling agents, such as silanes or titanates, may also be included in the
preparation of the rigid materials of the present invention to improve the
physical properties of the material by binding the hybrid resin more
strongly to the reinforcing particles.
Various methods for pretreating the various foamable composition
components, methods for producing the foam, and methods for forming the
foam into various structural shapes are disclosed in U.S. Ser. No.
08/348,973, which is hereby incorporated by reference.
Even when a foam is not desired, prior to being included in the curable
formulation of the present invention, the fine multisize reinforcing
particles are desirably subjected to a pretreatment process. Desirable
pretreatments of the particles may comprise grinding to a particle size
distribution consistent with that of fly ash or red mud, or drying, as
described in U.S. Ser. No. 08/348,973 for red mud.
The step of filling the material with the fine multisize reinforcing
particles does not appear to be time dependent, and the particular
placement of the reinforcing particles in part depends on the type of
metering, mixing, and dispensing equipment. In the simplest case, the
filling step comprises calculating a specific weight of reinforcing
particles based on the overall reactive polymer weight, to establish a
weight percent range (anywhere from 10% to 85%) preferably 60%; adding the
weighed particles to either the polyester polyol, diisocyanate or
polyisocyanate, or both; totally wetting out all reinforcing particles by
shear mixing, without inadvertently mixing the reactants; blending in any
special purpose reactive additive, e.g., a reactive flame retardant
polyol, a capped non-reactive polymer network to be further combined in an
IPN, etc.; and finally allowing air bubbles, which may have been mixed in,
to escape from the two blends, so that massive instabilities are not
present during curing. When a foam is desired, reinforcing particles
containing water as a blowing agent, or which are to be preloaded with a
blowing agent reactive with isocyanates should not, in general be added to
the isocyanate component, but should instead be premixed with the
polyester polyol component.
The mixing of the filled reactants is time dependent, and requires an
efficient shear mixer to homogeneously blend the thickened, filled
materials. The crosslinking reaction which occurs after the first sets of
reactions forming urethane and urea can be delayed to the point where
additional processing steps can be accomplished on the partially cured
mass.
Economic benefits related to machine capacity and mold filling requirements
result from using a filler system having relative amounts of either or
both reinforcing particles that can be tailored to control curing rates.
Specifically, smaller, less expensive metering, mixing, and dispensing
equipment can be used to fill molds that would normally require larger
machines due to a fixed, short reaction time after mixing.
The free radical initiated copolymerization of the reactive monomer and the
unsaturated polyester polyol occurs after the urethane reaction is well
underway. This crosslinking reaction significantly hardens the binder, and
is the final curing step, comprising reacting the ethylenically
unsaturated groups of unsaturated polyester-polyurethane and the reactive
monomer, which serves both as a diluent for the reaction system and as a
curing agent.
Examples of hybrid materials suitable for use as the unsaturated
polyester-polyurethane in the present invention are discussed in U.S. Ser.
No. 08/348,973, which is hereby incorporated by reference.
The selection of the particular fine multisize reinforcing particles,
dispersed filler particles, and optionally, any additional polymer forming
material to be included in the matrix, is in part dependent upon the
desired properties of the final product, and its intended use.
For example, in products where thermal expansion must be controlled, the
matrix should include epoxy resin networks, which may be bonded to,
crosslinked with, or intertwined with (as an IPN) the unsaturated
polyester-polyurethane resin. Fillers that bond well with epoxy should
also be used, such as carbon, ceramic, etc. In this way, preferably solid,
low coefficient of expansion products can be produced and used as
sheathing, slate, boards, or other products that must be secured by nails,
screws, or glue.
In products where flame retardency is desired, a flame retardant material,
such as scrap CPVC, can be used as the dispersed filler particles, and the
overall filler level can be increased. This material can then be used to
provide flame retardant materials, such as solid or foamed countertops,
for use inside the home.
Where a wear resistant surface is necessary, the overall filler level can
be increased, and a wear resistant polyurethane can be used as the
dispersed filler particles. In addition, the polyurethane percentage in
the binder can be increased. This material can be used for wear resistant
interior or exterior tiles, either in solid form or slightly foamed.
Where a weather resistant material is necessary, siloxane can be added to
the binder, the type and amount of filler can be selected to promote
staining, and the overall filler level can be increased. This material can
be used to prepare exterior products, both solid and foamed.
Furthermore, where the properties of two different dispersed filler
materials, or two different resin systems are desired in a single product,
the filler materials and/or the resin materials can be combined therein
with the unsaturated polyester-polyurethane containing resin and the fine
multisize reinforcing particles. For instance, an unsaturated
polyester-polyurethane-siloxane-epoxy containing matrix may be used in
applications that require a low expansion, high strength material having
good weatherability, such as decorative wear resistant tiles, hurricane
shutters, and other structural products.
In general, the materials of the present invention may be prepared by,
e.g., mixing the hybrid resin (or an unsaturated polyester polyol, a
saturated polyol, a poly- or diisocyanate, and a reactive monomer, all of
which react to form the hybrid resin), which is desirably diluted with
styrene, with a saturated polyol, the fine multisize reinforcing
particles, and the dispersed filler particles, and separately mixing a
polyisocyanate and a polymerization initiator, and then combining these
two mixtures just before molding to initiate polymerization. The material
is then allowed to cure in the mold, and removed therefrom. A silicone
surfactant may be included in the hybrid resin mixture to assist in mold
release, and other materials, such as pigments or colorants, may also be
included in these mixtures. If the unsaturated polyester-polyurethane
network is to contain domains bonded to other polymer resins, such as
epoxy resins, acrylic resins, vinyl ester resins, siloxane resins, or
combinations thereof, these resins or precursors thereof may be added,
desirably in liquid form, to the basic hybrid system prior to formation of
the complex crosslinked network, and may optionally be included with the
hybrid forming components and thus help to wet out the dry components.
In products wherein control of thermal expansion is important, an
open-weave fabric should be used as the dispersed filler particle, as this
significantly decreases the coefficient of thermal expansion.
The following nonlimiting examples indicate how to prepare composite
materials according to the present invention, and also provide a
methodology for determining the optimal combinations of dispersed filler
particles and matrix resins, using only the disclosure in this
specification and routine experimentation.
EXAMPLE 1
Four commercially available thermoplastic materials were purchased, and
included polyvinyl chloride sheet having a thickness of about 0.125 inch,
delrin (LEXAN) sheet having a thickness of about 0.125 inch, acrylic
rodstock having a diameter of about 3 inches, and reground scrap CPVC
plastic that normally would be landfilled. Two 4.times.4 inch squares were
removed from each of the sheet materials. Two plates of 3 inches diameter
and thickness of 0.250 inch were cut from the acrylic rod. The reground
scrap CPVC was not machined.
Four to five drops of a uninhibited styrene monomer, identical to that used
as a crosslinker and diluent for commercially available polyesters and
vinyl esters was placed on one surface of one of the polyvinyl chloride
sheets, and the remaining sheet was placed into contact therewith. This
procedure was followed for the delrin sheets and the acrylic plates.
A mixture of 30 grams of the reground scrap CPVC and 5 drops of styrene
were placed in the bottom of a small mold.
Slight pressure was applied to the specimens of all four materials for
three minutes. At the end of this time, the pressure was released. All
four materials were solvent bonded together.
This example illustrates the use of reactive monomer to wet out the
dispersed filler particles used in the present invention, and to solvent
bond the materials used in these dispersed filler particles, providing
adhesion between the dispersed filler particles and the continuous phase
matrix through the reactive monomer.
EXAMPLE 2
A combination of fly ash, CPVC reground plastic, and binder were mixed
according to the Table below.
______________________________________
SIDE A SIDE B
______________________________________
140 g unsaturated polyester
54 g polyisocyanate (5205,
polyol resin diluted with
Carpenter)
styrene (HC-100, Polymer
Development Lab.)
15 g saturated polyol
5 g benzoyl peroxide in
(5126, Carpenter) tricresyl phosphate (BPO,
Carpenter)
3 g silicone surfactant (DC
193, Air Products)
215 g Type F fly ash
475 g chlorinated polyvinyl
chloride chips
4 g coloring pigment
______________________________________
Side A was allowed to stand for three minutes, and was stable. After three
minutes, Side B was mixed with Side A. Because polymerization is initiated
at this point, the mixture must be poured into a mold within two minutes.
After curing, an inexpensive solid material was obtained containing over 80
percent by weight of filler and reinforcing particles which demonstrated
high compression strength and other desirable properties (such as tensile
strength, tensile modulus, flexural strength, flexural modulus, and
compression modulus) at low cost. Testing and examination of the material
indicated that many of the dispersed CPVC particles fractured when the
structure containing them was broken, indicating excellent chemical
bonding. Direct solvent bonding between dispersed particles was also
observed. The dispersed CPVC particles perform at least three functions in
the resulting composite: (a) providing the overall composite with
increased ductility; (b) providing a low cost method of obtaining desired
physical properties; and (c) providing the composite with excellent flame
retardency. In addition, their use in the composite eliminates material
that would have to be landfilled.
EXAMPLE 3
9 lbs of a mixture of hybrid resin containing 30 percent by weight of fly
ash and 1 percent by weight of Kevlar pulp was prepared according to the
table below.
______________________________________
SIDE A SIDE B
______________________________________
80.3 g unsaturated polyester
27.1 g. polyisocyanate
polyol resin diluted with
(5205, Carpenter)
styrene (5180, Carpenter)
18.1 g saturated polyester
4.0 g benzoyl peroxide in
polyol (5126, Carpenter)
tricresyl phosphate (BPO,
Carpenter)
1.6 g silicone surfactant
(DC 193, Air Products)
57 g Type F fly ash
1.9 g aramid based fiber,
1.5 mm thick (Kevlar,
DuPont)
______________________________________
The Side A components were mixed and allowed to thoroughly saturate or wet
out the Kevlar fibers. The mixture of Side A components and Kevlar fibers
became significantly thickened. The Side B components were mixed in a
separate vessel. The Side B mixture was added to the Side A mixture and
mixed thoroughly for 120 seconds.
The mixture was poured into a mold cavity 80 inches long, 19 inches wide,
and 1/8 inch thick. The mold was mounted in a Dake press capable of
exerting a pressure of 250 psi over the entire planar area of the mold.
The mold temperature was maintained at 205.degree. F. and the material
remained in the mold for 10 minutes. At the end of this time, the press
was opened and the material demolded in the form of a panel and allowed to
cool.
At a later date, the difference in the length of the panel at -10.degree.
F., and at 70.degree. F. was measured.
Upon heating to 70.degree. F., the panel had increased in length by 0.230
inches.
EXAMPLE 4
9 lbs of a mixture similar to that of Example 3, but modified by the
addition of commercially available vinyl ester (novolac epoxy based)
containing 30 percent by weight fly ash and 1 percent by weight of Kevlar
pulp was prepared according to the table below. This composition is the
same as in Example 3, except that the saturated polyester polyol (5126)
was replaced by a novolac epoxy based vinyl ester. Again, the mixture of
Side A components and Kevlar pulp became significantly thickened.
______________________________________
SIDE A SIDE B
______________________________________
80.3 g unsaturated polyester
21.8 g. polyisocyanate
polyol resin diluted with
(5205, Carpenter)
styrene (5180, Carpenter)
18.1 g novolac epoxy vinyl
4.0 g benzoyl peroxide in
ester (411-45, Dow)
tricresyl phosphate (BPO,
Carpenter)
1.6 g silicone surfactant
(DC 193, Air Products)
57 g Type F fly ash
1.9 g aramid based fiber,
1.5 mm thick (Kevlar,
DuPont)
______________________________________
The procedures set forth above in Example 3 were followed. The measured
change in length between -10.degree. F. and 70.degree. F. was 0.210 inch,
slightly less than that observed in Example 3.
This example indicates that the bonding between the Kevlar fiber and the
epoxy-containing resin is approximately equivalent to that between the
Kevlar fiber and the saturated polyester-containing resin.
EXAMPLE 5
9 lbs of a mixture of hybrid resin containing 30 percent by weight of fly
ash, 5 weight percent carbon fibers, and 2.5 weight percent ceramic fibers
was made according to the table below.
______________________________________
SIDE A SIDE B
______________________________________
80.3 g unsaturated polyester
27.1 g polyisocyanate (5205,
polyol resin diluted with
Carpenter)
styrene (5180, carpenter)
18.1 g saturated polyester
4.0 g benzoyl peroxide in
polyol (5126, Carpenter)
tricresyl phosphate (BPO,
Carpenter)
1.6 g silicone surfactant
(DC 193, Air Products)
52.1 g Type F fly ash
10.1 g carbon fiber, 180 m .times.
11 m, (VMX-Varx-24 thornel,
Amoco)
5 g fused silica alumina
ceramic fiber (bulk-KMTX,
Carborundum)
______________________________________
The Side A components were mixed and allowed to thoroughly saturate or wet
out the fiber additions. The Side B components were added to the Side A
components and mixed thoroughly for 120 seconds. The material was molded
by following the procedure set forth in Examples 3 and 4, above, except
that the mold temperature was 210.degree. F.
The change in length upon heating from -10.degree. F. to 70.degree. F. was
0.141 inches, which is a significant improvement over the changes observed
in Examples 3 and 4. This 39% reduction in expansion is not the result of
the change in filler alone, and indicates that there is either improved
bonding between the matrix and the fibers, or a fiber interaction, or
both, that results in this improved reduction in expansion.
EXAMPLE 6
9 lbs. of a mixture of hybrid modified by substituting the commercially
available vinyl ester novolac epoxy resin of Example 4 for the saturated
polyol and containing 30 percent by weight of fly ash, 5 weight percent
carbon fibers, and 2.5 weight percent ceramic fibers was made according to
the table below.
______________________________________
SIDE A SIDE B
______________________________________
80.5 g unsaturated polyester
21.8 g polyisocyanate (5205,
polyol resin diluted with
Carpenter)
styrene (5180, Carpenter)
18.1 g novolac epoxy vinyl
4.0 g benzoyl peroxide in
ester (411-45, Dow)
tricresyl phosphate (BPO,
Carpenter)
1.6 g silicone surfactant
(DC 193, Air Products)
62.1 g Type F fly ash
10.1 g carbon fiber, 180 m .times.
11 m, (VMX-Varx-24 thornel,
Amoco)
5 g fused silica alumina
ceramic fiber (bulk-KMTX,
Carborundum)
______________________________________
The procedure followed was the same as that used in Example 5, except that
the mold temperature was 205 .degree. F.
The change in length from -10.degree. F. to 70.degree. F. was 0.094 inch, a
reduction equivalent to many fiberglass BMC materials. This represents a
55% reduction in expansion compared to Example 4. This 55% reduction is
not explainable by the change in filler level or by fiber interactions,
since a 0.094 inch change in length was not exhibited by Example 5. The
expansion reduction is due to the excellent bonding between the novolac
epoxy vinyl ester resin with one or both of the fiber additives.
As the above Examples 2-6 show, the addition of specific polymer forming
materials to the composition results in products wherein those polymers
not only affect the physical and chemical properties of the matrix, but
react with the dispersed filler particles (and in some instances with the
fine multisize reinforcing particles as well). For example, Kevlar fibers
exhibited no significant difference in properties when used in a matrix
containing an epoxy resin, as compared to a matrix containing a saturated
polyester resin (compare Example 3 and Example 4). However, by selecting a
ceramic fiber and a carbon fiber as the dispersed filler materials and an
epoxy containing resin as the matrix material, significant decreases in
thermal expansion are obtained (compare Example 6 to Examples 3, 4, and
5). The examples show that the fine multisize reinforcing particle filled
unsaturated polyester-polyurethane containing resin of the presently
claimed invention provides an adaptable starting point for the inclusion
of dispersed filler particles which can be made to preferentially react
with the unsaturated polyester-polyurethane resin itself, or with optional
additional polymer components, either through direct chemical bonding or
crosslinking therewith. This allows for excellent properties and for
excellent control thereover.
EXAMPLE 7
In vessel 1, a multipolymer system containing a unsaturated polyester
hybrid polyol resin was blended with a novolac epoxy based vinyl ester.
Additionally, Type F fly ash was added in sufficient amount that the
weight percent of this component would equal 50 weight percent of the
final mixture. Independently, in vessel 2 a methylene diphenyl isocyanate
was blended with 50% benzoyl peroxide paste. The relative amounts of each
component is given below.
______________________________________
Vessel 1 Vessel 2
______________________________________
148 g unsaturated polyester
44 g methylene diphenyl
polyol (Carpenters 5180)
isocyanate
22 g novolac epoxy based vinyl
6 g 50% benzoyl peroxide paste
ester (Dow Duracane 411-45)
220 g Type F fly ash
______________________________________
The materials in each vessel are mixed independently, and then the contents
of each vessel are combined and placed in a mold, wherein polymerization
is initiated. Within ten minutes, the liquid in the mixture has
polymerized to a solid, evenly crosslinked thermoset polymer, which
contains urethane components, unsaturated polyester components, and epoxy
components. Not only is its heat resistance significantly increased when
compared to compositions made from the hybrid resin alone, but additional
reinforcement potentials are possible due to the integral epoxy component,
which is fully crosslinked into the polymer. The coefficients of thermal
expansion of the resulting material is significantly reduced as compared
to that of either the epoxy resin or the hybrid resin, individually.
EXAMPLE 8
The same procedure was followed as in Example 7, except that an open-weave
ceramic fiber mat (250 square mesh, basalt) is placed in the mold. The
highly filled mixed liquid obtained by mixing the contents of vessel 1 and
vessel 2 is poured over the ceramic fiber mat and allowed to polymerize.
Upon curing, it is found that excellent bonding has occurred between this
polymer mixture and the fiber components. The excellent chemical
compatibility between the components of the hybrid mix and the novolac
epoxy based composition allows the formation of a material containing
epoxy that bonds better to many ceramic materials than the hybrid resin
alone. This is due to both the compatibility of certain sizing compounds
to ceramic compositions and to the inherent high bond strengths of epoxy
compounds to refractory compositions.
EXAMPLE 9
The procedure followed in Example 8 was repeated, except that the mold
contained an alumina silica refractory blend (Carborundum, bulk-EF122S)
made into a very loose mat. Excellent bonding between the highly filled
polymer material and the ceramic material was also observed.
EXAMPLE 10
In vessel 1, a multipolymer system containing a unsaturated polyester
hybrid polyol resin was blended with a novolac epoxy based vinyl ester.
Additionally, Type F fly ash and sized slate chips were added in
sufficient amount that the weight percent of these components would equal
85 weight percent of the final mixture. Independently, in vessel 2 a
methylene diphenyl isocyanate was blended with 50% benzoyl peroxide paste.
The relative amounts of each component is given below.
______________________________________
Vessel 1 Vessel 2
______________________________________
148 g unsaturated polyester
44.1 g methylene diphenyl
polyol (Carpenters 5180)
isocyanate
22 g novolac epoxy based vinyl
6 g 50% benzoyl peroxide paste
ester (Dow Duracane 411-45)
240 g Type F fly ash
1050 g needle-like slate chips,
which were sized to pass
through 0.0937 inch mesh and
not pass through 0.078 inch
mesh (obtained from LeSeur-
Richmond Slate Corp.)
______________________________________
The materials in each vessel are mixed independently, and then the contents
of each vessel are combined (vessel 2 is added to vessel 1) and mixed for
90 seconds. The mixed contents were poured into a 10 inch.times.16
inch.times.0.187 inch lined mold and vibrated flat. A solid, fully cured
mass bearing a very close resemblance to actual slate was produced. Not
only did the overall solid possess excellent resistance to heat, but the
needle-like slate particles were well bonded to the matrix, and provided
additional tensile and impact strength to the filled structure. The
overall density of the material was 120 lb/ft.sup.3, approaching that of
actual slate.
A two part experiment was conducted to show the wide range of chemical
changes possible with the polyurethane/unsaturated polyester hybrid
structure and the effect that these changes have on chemical bonding in
the resulting product. Example 11 involves the addition of a thermoset
novolac vinyl ester polymer that should bond chemically with reinforced
and nonreinforced pellets of thermoplastic ABS
(acrylonitrile-butadiene-styrene). In Example 12, the epoxy component was
eliminated, and a polyol was added that reacts with isocyanate to form a
ductile urethane. In this example, the hybrid contained a higher urethane
percentage than in Example 11, and as a result, interfacial bond strengths
were expectedly lower. Because the reinforced and nonreinforced ABS
pellets were different in color, qualitative observations could also be
made.
EXAMPLE 11
In vessel 1, a multipolymer system containing a unsaturated polyester
polyol was blended with a novolac epoxy based vinyl ester. Additionally,
Type F fly ash and mixed pellets of reinforced and nonreinforced ABS were
added. The total percentage of fly ash and ABS particles approximated 70
percent by weight of the final mixture. Independently, in vessel 2 a
methylene diphenyl isocyanate was blended with 50% benzoyl peroxide paste.
The relative amounts of each component is given below.
______________________________________
Vessel 1 Vessel 2
______________________________________
100 g unsaturated polyester
28 g methylene diphenyl
polyol (Carpenters 5180)
isocyanate
40 g novolac epoxy based vinyl
6 g 50% benzoyl peroxide paste
ester (Dow Duracane 411-45)
176 g Type F fly ash
176 g mixed glass reinforced
and nonreinforced ABS pellets
(cylindrical, 0.13 in diameter,
0.19 in length, obtainable from
various manufacturers)
______________________________________
The materials in each vessel are mixed independently, and then the contents
of each vessel are combined and mixed, whereupon polymerization was
initiated. The mixed material was immediately poured into tensile bar
molds and a flat plate mold. The mixture hardened within 10 minutes, and
was post cured for 1 hour at 250.degree. F. Cured samples were tested to
failure, and the fracture surfaces observed. About 70-80 percent of the
samples containing nonreinforced ABS pellets sheared throughout, and about
50 percent of the materials containing the glass reinforced ABS sheared,
while the remaining 50% showed particles which pulled out of the matrix.
Overall, the chemical bonding was excellent.
EXAMPLE 12
In vessel 1 a two polymer system containing a high percentage of a urethane
former was blended with fly ash and mixed glass reinforced and
nonreinforced ABS pellets. The epoxy component used in Example 11 was not
added. However, the total percentage of filler and reinforcing particles
was maintained at 70 percent by weight. Independently, in vessel 2 a
methylene diphenyl isocyanate was blended with 50% benzoyl peroxide paste.
The relative amounts of each component is given below.
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Vessel 1 Vessel 2
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100 g unsaturated polyester
39 g methylene diphenyl
polyol (Carpenters 5180)
isocyanate
40 g saturated polyester polyol
4 g 50% benzoyl peroxide paste
(Carpenters 5126)
185 g Type F fly ash
185 g mixed glass reinforced
and nonreinforced ABS pellets
(cylindrical, 0.13 in diameter,
0.19 in length, obtainable from
various manufacturers)
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The materials in each vessel are mixed independently, and then the contents
of each vessel are combined and mixed, whereupon polymerization was
initiated. The mixed material was immediately poured into tensile bar
molds and a flat plate mold. The mixture hardened within 10 minutes, and
was post cured for 1 hour at 250.degree. F. Cured samples were tested to
failure, and the fracture surfaces observed. In contrast to Example 11,
about 40-50% of the nonreinforced pellets sheared through. 100% of the
reinforced pellets pulled out of the matrix, indicating lower interfacial
bond strengths than in Example 11. However, a much more ductile
polyurethane/unsaturated polyester hybrid is obtained.
Foamed materials within the scope of the present invention can be prepared
by using fine multisize reinforcing particles having an entrained blowing
agent, and/or capable of releasing the blowing agent to the matrix system
as it is forming, in accordance with the teachings of U.S. Ser. No.
08/348,973 and U.S. Pat. Nos. 5,369,147 and 5,302,634, which are hereby
incorporated by reference.
The products of the present invention may be used, e.g., as building
materials, e.g., as solid roofing materials (e.g., slates or tiles, which
are lightweight in the foamed form), as decorative or architectural
products, as outdoor products, as low cost insulation panels, as fencing,
as buoyant or corrosion-resistant marine products, etc., by forming the
resin in a mold of suitable size and shape, according to art recognized
methods and then using the molded product in an art-recognized way.
For example, non-filler specific uses include sheet materials for use in
composite structures (both solid and foamed); nonstructural products
(e.g., interior and exterior moldings, picture frames, decorative and
architectural products, and mantles); and cast structures that do not have
critical requirements for their physical or chemical properties (e.g.,
sink tops, interior corrosion resistant tiles, etc.).
Materials containing specific fillers or specific polymer networks in the
matrix may be used in applications requiring the properties provided by
those fillers and the particular matrix phase. For example, open weave
fabrics, or ceramic and carbon fibers as dispersed filler materials
combined with an unsaturated polyester-polyurethane-epoxy resin system can
be used in applications requiring control of thermal expansion.
Plastic scrap having particular properties, such as the fire resistance
possessed by CPVC can be used as the dispersed filler particles in matrix
systems containing a reactive monomer, such as styrene or known adhesive
components which are present along with the hybrid forming components, and
that bond well with the particle material.
Matrix materials containing an unsaturated polyester-polyurethane-siloxane
in the matrix material provide excellent UV stability and a flexible
bonding agent. In addition, these siloxane-containing matrices bond well
with both fly ash (as the fine multisize reinforcing particles) and
ceramic or glassy dispersed filler particles, as well as with metals,
paper, and many thermosetting material-containing elastomers (e.g., cured
SRIM scrap containing glass fiber). These products can be used as exterior
molding, tiles, pool tiles, window trim, and decorative shutters.
Structural uses are also possible.
The present invention allows for the conversion of a number of different
types of waste material, both in the form of time multisize reinforcing
particles and as dispersed filler particles, into a value-added, useful
material having superior properties, while at the same time avoiding the
social and economic costs associated with disposal of this material.
The invention being thus described, it will be obvious that the same may be
varied in many ways. Such variations are not to be regarded as a departure
from the spirit and scope of the invention, and all such modifications as
would be obvious to one skilled in the art are intended to be included
within the scope of the following claims.
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